EP3515991B1 - Naphthopyrannes photochromiques à multiples condensations de noyaux offrant une absorption de très grandes longueurs d'ondes allant loin dans les longueurs d'ondes du domaine visible - Google Patents

Naphthopyrannes photochromiques à multiples condensations de noyaux offrant une absorption de très grandes longueurs d'ondes allant loin dans les longueurs d'ondes du domaine visible Download PDF

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EP3515991B1
EP3515991B1 EP17731064.6A EP17731064A EP3515991B1 EP 3515991 B1 EP3515991 B1 EP 3515991B1 EP 17731064 A EP17731064 A EP 17731064A EP 3515991 B1 EP3515991 B1 EP 3515991B1
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EP3515991A1 (fr
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Udo Weigand
Herbert Zinner
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Rodenstock GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters

Definitions

  • the present invention relates to photochromic multiple-fused naphthopyrans with very long-wave absorption of the closed form well into the visible wavelength range and their use in plastics of all kinds, in particular for ophthalmic purposes, preferably in driver's glasses.
  • the compounds according to the invention also have a very good life with very high performance.
  • Pyrans especially naphthopyrans and larger ring systems derived from them, are currently the most studied class of photochromic compounds. Although a patent was first applied for in 1966 ( U.S. 3,567,605 ), it was not until the 1990s that compounds could be developed that appeared suitable for use in spectacle lenses.
  • a suitable compound class of pyrans are, for example, the 2,2-diaryl-2H-naphtho [1,2-b] pyrans or the 3,3-diaryl-3H-naphtho [2,1-b] pyrans, which are in excited form have different darkening colors from yellow to red.
  • Fused naphthopyrans derived from these basic systems are extremely interesting, because of their larger ring system they absorb longer waves and produce red, violet and blue darkening colors. This will be Usually a benzene ring with an additional bridge in the ortho position (the bridge with the substituents R 1 and R 2 in the compounds according to the invention below) is used.
  • EP 2 457 915 , EP 2 471 794 , EP 2,684,886 , EP 2 788 340 as EP 2,872,517 compounds are disclosed in which at least one further ring system is fused to the indenonaphthopyran core structure, but in contrast to the compounds according to the invention of the formula (I) below, to the CC bond between the substituents R 7 and R 10 , ie at a different point the core structure.
  • the annealing at this point results in a significantly smaller bathochromic shift of the longest-wave absorption band compared to the compounds of the formula (I) according to the invention below.
  • EP 0 912 908 compounds are also listed in which two further ring systems are fused to the indenonaphthopyran core structure, ie at the same point as in the following compounds of the formula (I) according to the invention.
  • the annellations described bring about a significantly smaller bathochromic shift of the longest-wave absorption band of the closed form compared to the compounds of the formula (I) according to the invention.
  • EP 1 097 156 describes compounds with a diatomic bridge of one carbon and one oxygen atom, as well as EP 2 178 883 and EP 2,760,869 .
  • the present invention is therefore based on the object of providing photochromic dyes which are to be distinguished by long-wave absorption of the closed form, which extends far into the violet or blue visible wavelength range.
  • the compounds according to the invention are distinguished by the fact that at least two further ring systems are fused to the C — C bond of the benzene ring adjacent to the substituent R 3 on an indenonaphthopyran core structure.
  • the longest-wave absorption band of the closed form of these photochromic dyes is shifted bathochromically to such an extent that it extends far into the violet or blue visible wavelength range.
  • the compounds according to the invention therefore require the transition to the excited (colored) form available photochromic dyes no or hardly any UV light and therefore darken, for example, behind a car windshield, which completely absorbs UV light. In this way, for example, driver glasses can be produced that darken deeply even in the closed car when the sun shines directly through the completely UV-absorbing windshield.
  • the compounds according to the invention are also distinguished by their excellent UV curing compatibility, i. they survive - introduced e.g. in an acrylate monomer matrix with UV initiator - without prejudice to radical polymerisation of the matrix triggered by strong UV light. In addition, they have a very good service life with very high performance. They can be used in all types of plastics.
  • the molecular structure of the compounds according to the invention is based on an indenonaphthopyran core structure (each with the substituents R 1 , R 2 , R 3 , R 7 and R 10 in the formulas), which contains the photolabile pyran unit (with the substituents B and B ') contains. This is responsible for the photochromic character, since light excitation reversibly breaks the bond between the oxygen of the pyran unit and the carbon atom with the substituents B and B ', creating a colored merocyanine system.
  • the present invention is based on the surprising finding that, in the case of multiple annulation to the indenonaphthopyran core structure, the longest-wave absorption band of the closed form of the photochromic compounds according to the invention can be shifted bathochromically that it extends far into the violet or . the blue visible wavelength range extends into. This fact could be achieved in two ways.
  • compounds of the formula (I) which have an annulation of at least two further ring systems (with X 'and the substituents R 4 ) to the CC bond of the benzene ring adjacent to the substituent R 3 .
  • the radicals R 1 , R 2 , R 3 , R 4 , R 7 , R 8 and R 10 are independently of one another from a hydrogen atom, a (C 1 -C 6 ) -alkyl radical or a (C 3 -C 7 ) -cycloalkyl radical selected.
  • X 'in the formula (I) is selected from -CH 2 -, -C (CH 3 ) 2 -, -C (C 2 H 5 ) 2 -, -C (C 6 H 5 ) 2 -, -O-CH 2 - or -CH 2 -O- is selected.
  • X in formula (II) or (III) is selected from -O-, -S-, -CH 2 -, -C (CH 3 ) 2 -, -C (C 2 H 5 ) 2 -, -C (C 6 H 5 ) 2 -, -O-CH 2 -, -CH 2 -O-, -CH 2 -CH 2 -, -C (CH 3 ) 2 -CH 2 - or - CH 2 -C (CH 3 ) 2 - selected.
  • Y and Z are independently selected from -O-, -CH 2 -, -C (CH 3 ) 2 -, -C (C 2 H 5 ) 2 - or -C (C 6 H 5 ) 2 -selected, where Y or Z in turn, optionally together with the respectively adjacent CR 5 R 6 group, can form a fused benzene ring which can be un-, mono- or disubstituted, the substituents in turn being able to be selected from the group ⁇ .
  • the R 9 radical is preferably a (C 1 -C 18 ) -alkyl radical, a phenyl radical or a benzyl radical.
  • radicals B and B ' are selected independently of one another from group a), as defined above.
  • the photochromic multiply fused naphthopyrans according to the invention have the general formula (I).
  • Figure 1 shows the absorption spectra (400-480 nm) of compounds according to the invention in the closed form (non-excited state) in comparison with the prior art EP 0 912 908 .
  • the longest-wave absorption band of the closed form of the compounds according to the invention is shifted significantly towards longer wavelengths compared to the prior art.
  • the compounds according to the invention also darken well behind a completely UV-absorbing car windshield (see Table 1).
  • the difference in saturation absorption between the standard measurement (without GG400 filter) and the measurement with GG400 filter is a meaningful parameter.
  • the smaller this difference the less UV light below 400 nm is required for darkening and the more suitable the photochromic dye is for use in driver's glasses.
  • the compounds according to the invention all have a significantly lower difference value compared to compounds of the prior art and require practically no UV light below 400 nm for darkening.
  • step (i) suitably substituted methylidene succinic anhydrides are subjected in a first step to a Friedel-Crafts reaction with suitably substituted aromatic systems (step (i)).
  • step (i) suitably substituted aromatic systems
  • step (ii) The —COOH group of the intermediate resulting therefrom is then protected and this intermediate is subjected to a Michael addition with appropriately substituted aryl Grignard compounds (step (ii)).
  • step (iii) After the carboxylic acid protective group has been removed, correspondingly substituted naphthol derivatives are formed via intramolecular cyclization using phosphoric acid (step (iii)). These are then reacted with suitably substituted 2-propyn-1-ol derivatives according to step (iv) to give the compounds according to the invention.
  • the compounds according to the invention can be used in plastic materials or plastic objects of any type and shape for a large number of purposes for which photochromic behavior is important.
  • a dye according to the present invention or a mixture of such dyes can be used.
  • the photochromic naphthopyran dyes according to the invention can be used in lenses, in particular ophthalmic lenses, glasses for glasses of all kinds, such as ski goggles, sunglasses, motorcycle goggles, visors for protective helmets and the like, especially in driver's glasses.
  • the photochromic naphthopyrans according to the invention can also be used, for example, as sun protection in vehicles and living spaces of windows, protective shutters, covers, roofs or the like.
  • the photochromic naphthopyrans according to the invention can be used by various processes described in the prior art, as already described in WO 99/15518 specified, applied to or embedded in a polymer material such as an organic plastic material.
  • a bulk coloring process comprises, for example, dissolving or dispersing the photochromic compound or compounds according to the present invention in a plastic material, for example by adding the photochromic compound (s) to a monomeric material before the polymerization takes place.
  • Another possibility for producing a photochromic object is the penetration of the plastic material (s) with the photochromic compound (s) by immersing the plastic material in a hot solution of the photochromic dye (s) according to the present invention or, for example, a thermal transfer process.
  • the photochromic compound (s) can, for example, also be provided in the form of a separate layer between adjacent layers of the plastic material, for example as part of a polymeric film.
  • photochromic compound (s) as part of a coating on the surface of the plastic material.
  • penetration is intended to mean the migration of the photochromic compound (s) into the plastic material, for example through the solvent-assisted transfer of the photochromic compound (s) into a polymer matrix, vapor phase transfer or other such surface diffusion processes.
  • photochromic objects such as spectacle lenses, can be produced not only by means of the usual mass coloring, but also in the same way by means of surface coloring, with the latter variant being able to achieve a surprisingly lower tendency to migrate. This is above all This is an advantage in subsequent finishing steps, as, for example, in the case of an anti-reflective coating due to the lower back diffusion in a vacuum, delamination and similar defects are drastically reduced.
  • any compatible (chemically and color-compatible) colorations i.e. Dyes, applied to or embedded in the plastic material in order to satisfy aesthetic considerations as well as medical or fashionable aspects.
  • the specifically selected dye (s) may therefore vary depending on the intended effects and requirements.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Eyeglasses (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Optical Filters (AREA)
  • Pyrane Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Glass Compositions (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Claims (11)

  1. Naphtopyranes photochromiques multi-condensés de formules (I), (II) ou (III):
    Figure imgb0008
    dans lesquels les radicaux R1, R2, R3, R4, R7, R8 et R10 représentent chacun indépendamment un substituant choisi dans le groupe a, consistant en un atome d'hydrogène, un radical (C1-C18) alkyle, un (C3-C7) cycloalkyle, qui peut avoir un ou plusieurs hétéroatomes, tels que O ou S, un radical thioalkyle (C1-C18), un radical (C1-C18) alcoxy, un groupe hydroxy, un groupe trifluorométhyle, brome, chlore, fluor, un , un radical phényle, phénoxy, benzyle, benzyloxy, naphtyle ou naphtoxy mono- ou disubstitué, ces substituants étant choisis dans le groupe β, constitué par un atome d'hydrogène, un radical (C1-C6) alkyle, un (C3-C7) cycloalkyle , un radical (C1-C6) thioalkyle, un radical (C1-C6) alcoxy, un radical phényle, un radical benzyle ou un radical naphtyle;
    n représente un entier de 1 à 4;
    ou les radicaux R1 et R2 avec l'atome de carbone lié à ces radicaux forment un cycle carbo- ou hétéromonocyclique à trois à huit chaînons qui porte éventuellement un ou plusieurs substituants du groupe β et sur lequel un à trois systèmes cycliques aromatiques ou hétéroaromatiques peuvent être condensés, où le ou les systèmes cycliques sont choisis indépendamment parmi le benzène, le naphtalène, le phénanthrène, la pyridine, la quinoléine, le furane, le thiophène, le pyrrole, le benzofurane, le benzothiophène, l'indole et le carbazole, qui peuvent être substitués par un ou plusieurs substituants choisis parmi le groupe β;
    ou deux radicaux adjacents R4 forment un cycle benzénique condensé qui peut être non substitué, mono- ou disubstitué, les substituants pouvant être choisis dans le groupe β;
    ou deux radicaux adjacents R4 forment un système cyclique 1,1-diméthylindène ou benzofurane fusionné via la double liaison dans le cycle à cinq chaînons;
    ou deux radicaux adjacents R4 forment un système cyclique 2H-chromène ou 1 H-isochromène fusionné via la double liaison dans le cycle hétérocyclique à six chaînons, les radicaux R5 et R6 représentent chacun indépendamment un substituant choisi parmi l'hydrogène et un radical (C1-C18) alkyle, un radical phényle, un radical benzyle ou un radical naphtyle;
    m représente un entier de 1 à 4, de préférence 1 ou 2, mieux encore 2;
    ou deux groupes -CR5R6- adjacents forment un cycle benzène condensé qui peut être non substitué, mono- ou disubstitué, les substituants étant choisis dans le groupe β;
    le radical Rg représente un substituant choisi parmi l'hydrogène, un radical (C1-C18) alkyle, un radical phényle, un radical benzyle ou un radical naphtyle; X 'dans la formule (I) est choisi parmi -SO2-, -CH2-, -C(CH3)2-, -C(C2H5)2-, -C(C6H5)2-, -O-CH2-, -CH2-O-, -CH2-CH2-, - C(CH3)2-CH2- ou -CH2-C(CH3)2-;
    X dans la formule (II) ou (III) est choisi parmi -O-, -S-, -SO2-, -N(C1-C6)-Alkyl-, -NC6H5-, - CH2-, -C(CH3)2-, -C(C2H5)2-, -C(C6H5)2-, -O-CH2-, -CH2-O-, -O-(C=0)-, -(C=O)-O-, -CH2-CH2-, -C(CH3)2-CH2- ou -CH2-C(CH3)2-;
    Y et Z sont choisis indépendamment parmi -O-, -S-, -SO2-, -N(C1-C6)-Alkyl-, -NC6H5-, -CH2-, -C(CH3)2-, -C(C2H5)2- ou -C(C6H5)2-, où Y ou Z, éventuellement conjointement avec le groupe CR5R6 adjacent, peuvent former un cycle benzène condensé qui peut être non substitué, mono- ou disubstitué, où les substituants sont choisis dans le groupe β, ou Y ou Z conjointement avec le groupe CR5R6 adjacent forment un système cyclique condensé naphtalène, 9,9-diméthylfluorène ou dibenzofurane, où un ou plusieurs substituants peuvent être substitués, choisis dans le groupe β;
    et dans laquelle B et B 'sont choisis indépendamment parmi l'un des groupes a) ou b) suivants, où
    a) est un radical aryle mono-, di- et trisubstitué, le radical aryle étant phényle, naphtyle ou phénanthryle, et
    b) est un radical hétéroaryle non substitué, mono- et disubstitué, le radical hétéroaryle étant choisi parmi pyridyle, furanyle, thiényle, benzofuranyle, benzothiényle, 1,2,3,4-tétrahydrocarbazolyle ou julolidinyle;
    où les substituants des radicaux aryle et hétéroaryle en a) et b) sont choisis dans le groupe β ou le groupement -(O-CHR13-CH2)q-OR14, où R13 représente l'hydrogène ou un radical méthyle, R14 représente l'hydrogène ou représente un (C1-C6) alkyle et q représente un entier de 1 à 50;
    ou les substituants en a) et b) sont choisis dans le groupe χ, consistant en amino, mono- (C1-C18) -alkylamino, di- (C1-C18) -alkylamino, phénéthényle qui est non substitué, mono- ou disubstitué sur le cycle phényle, (phényl-imino) méthylène non substitué, mono- ou disubstitué, non substitué, mono- ou disubstitué (phénylméthylène) imino et mono- et diphénylamino non substitué, mono- ou disubstitué, pipéridinyle, 3,5-diméthylpipéridinyle , Pipérazinyle N-substitué, pyrrolidinyle, imidazolidinyle, pyrazolidinyle, indolinyle, morpholinyle, 2,6-diméthylmorpholinyl, thiomorpholinyle, azacycloheptyle, azacyclooctyle, phénothiazinyle non substitué, mono- ou disubstitué, phénothiazinyle non substitué, mono- ou disubstitué, phénothiazinyle non substitué, mono- ou disubstitué 9,10-dihydroacridinyle, non substitué, mono- ou disubstitué 1,2,3,4-tétrahydroquinolinyle, 2,3-dihydro-1,4-benzoxazinyle non, mono- ou disubstitué, non substitué, mono- ou disubstitué 1 , 2,3,4-tétrahydroisoquinolinyle, phénazinyle non substitué, mono ou disubstitué, carbazolyle non substitué, mono- ou disubstitué, non substitué, mono- ou disubstitué 1, 2, 3,4-tétrahydrocarbazolyle et 10,11-dihydrodibenz [b, f] azépinyle non substitué, mono- ou disubstitué, où le ou les substituants peuvent à leur tour être choisis indépendamment l'un de l'autre dans le groupe β;
    ou deux substituants directement adjacents des radicaux aryle et hétéroaryle en a) et b) représentent un groupement V-(CR11R12)P-W, où p représente un entier de 1 à 3, les radicaux R11 et R12 chacun indépendamment l'un de l'autre un substituant, choisis dans le groupe β, et V et W indépendamment l'un de l'autre parmi -O-, -S-, -N (C1-C6) -alkyl-, - NC6H5-, -CH2-, -C(CH3)2-, -C(C2H5)2- ou -C(C6H5)2-;
    ou deux ou plusieurs groupes CR11R12 adjacents font partie d'un cycle benzène condensé, qui peut être non substitué, mono- ou disubstitué, les substituants étant à leur tour choisis dans le groupe β;
    ou V et / ou W conjointement avec le groupe CR11R12 respectivement adjacent forment un cycle benzène condensé qui peut être non substitué, mono- ou disubstitué, les substituants étant à leur tour choisis dans le groupe β.
  2. Naphtopyranes photochromiques multi-condensés selon la revendication 1, dans lesquels les radicaux R1, R2, R3, R4, R7, R8 and R10 sont choisis indépendamment l'un de l'autre parmi un atome d'hydrogène, un radical alkyle en (C1-C6) ou un radical cycloalkyle en (C3-C7).
  3. Naphtopyranes photochromiques multi-condensés selon la revendication 1 ou 2, dans lesquels X' dans la formule (I) est choisi parmi -CH2-, -C(CH3)2-, -C(C2H5)2-, -C(C6H5)2-, -O-CH2- ou -CH2-O-.
  4. Naphtopyranes photochromiques multi-condensés selon la revendication 1 ou 2, dans lesquels X dans la formule (II) ou (III) est choisi parmi -O-, -S-, -CH2-, -C(CH3)2-, -C(C2H5)2-, - C(C6H5)2-, -O-CH2-, -CH2-O-, -CH2-CH2-, -C(CH3)2-CH2- ou -CH2-C(CH3)2-.
  5. Naphtopyranes photochromiques multi-condensés selon la revendication 1, 2 ou 4, dans lesquels Y et Z sont choisis indépendamment parmi -O-, -CH2-, -C(CH3)2-, -C(C2H5)2- ou - C(C6H5)2-, où Y ou Z, éventuellement conjointement avec le groupe CR5R6 adjacent respectif, peuvent former un cycle benzène condensé qui peut être non substitué, mono- ou disubstitué, les substituants étant à leur tour choisis dans le groupe β.
  6. Naphtopyranes photochromiques multi-condensés selon la revendication 1, 2 ou 3, dans lesquels le radical Rg est un radical (C1-C18) alkyle, un radical phényle ou un radical benzyle.
  7. Naphtopyranes photochromiques multi-condensés selon l'une des revendications précédentes, dans lesquels les radicaux B et B 'sont choisis indépendamment l'un de l'autre dans le groupe a) tel que défini ci-dessus.
  8. Naphtopyranes photochromiques multi-condensés selon l'une des revendications précédentes, répondant à la formule générale (I).
  9. Naphtopyranes photochromiques multi-condensés selon l'une des revendications précédentes, répondant à la formule générale (IV), (V) ou (VI),
    Figure imgb0009
     où X' et X sont tels que définis ci-dessus.
  10. Utilisation des naphtopyranes photochromiques multi- condensés selon l'une des revendications 1 à 9 dans et sur des matières plastiques.
  11. Utilisation selon la revendication 10, dans laquelle la matière plastique est une lentille ophtalmique, en particulier pour des lunettes de conduite.
EP17731064.6A 2016-09-26 2017-05-23 Naphthopyrannes photochromiques à multiples condensations de noyaux offrant une absorption de très grandes longueurs d'ondes allant loin dans les longueurs d'ondes du domaine visible Active EP3515991B1 (fr)

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PCT/EP2017/000617 WO2018054507A1 (fr) 2016-09-26 2017-05-23 Naphthopyrannes à multiples condensations de noyaux, et photochromiques offrant une absorption de très grandes longueurs d'ondes allant loin dans les longueurs d'ondes du domaine visible

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US10647852B2 (en) 2020-05-12
IL265577A (en) 2019-05-30
IL265577B (en) 2022-07-01
US20190284397A1 (en) 2019-09-19
EP3515991A1 (fr) 2019-07-31
JP2019537554A (ja) 2019-12-26
JP6949946B2 (ja) 2021-10-13
WO2018054507A1 (fr) 2018-03-29

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